High pressure NMR investigation on o-bond coordination in organometallic chemistry and catalysis

• Research unit: COST
• Project number: C96.0036

Key words (English)

High pressure; NMR; Gas; Kinetics; Reaction Mechanism

Research programs (English)

COST-Action D6 - Chemical processes and reactions under extreme or non-classic conditions

Short description (English)

See abstract

Partners and International Organizations (English)

B, CH, CZ, D, DK, E, F, FIN, GR, H, I, NL, P, PL, S, SI, SK

Abstract (English)

A new high pressure NMR gas reactor (HPG-NMR probe) was built to fit in a standard bore, 9.4 Tesla cryomagnet. The probe is designed to work at gas pressure up to 1000 bar and at temperature up to 150 0C. The probe can also be used for work with hydrostatic pressure up to 2000 bar. A removable mixing unit assures rapid dissolution of the gas in the solution. This probe is suitable for multinuclear NMR (i.e. 13C, 170, 31P etc.) including the possibility for 1H decoupling and 2H field lock. Improvement of high pressure NMR sapphire tubes (100 bar), for better spinning, security and handling was also performed The high pressure NMR probe was used for mechanistic investigations. We have successfully determined kinetic parameters for water exchange in the ionic species [Pt{C6H3(CH2N Me2)2-2,6}(0H2))+(OSO2CF3{ using high pressure 170 NMR spectroscopy. A surprising fast water exchange rate on a Pt(ll) centre was observed and the mechanism was found to be associative and the influence of the para-substituent in the aryl-ring on the water exchange rate was studied. The complex formation reaction of [Ru(H20)6]2+ with ethylene was investigated at variable temperature and gas pressure up to 400 bar (gas concentration).

References in databases (English)

Swiss Database: COST-DB of the State Secretariat for Education and Research Hallwylstrasse 4 CH-3003 Berne, Switzerland Tel. [phone] Swiss Project-Number: C96.0036